CA1234655A - Method of peroxide bleaching cellulose-containing material - Google Patents

Method of peroxide bleaching cellulose-containing material

Info

Publication number
CA1234655A
CA1234655A CA000443564A CA443564A CA1234655A CA 1234655 A CA1234655 A CA 1234655A CA 000443564 A CA000443564 A CA 000443564A CA 443564 A CA443564 A CA 443564A CA 1234655 A CA1234655 A CA 1234655A
Authority
CA
Canada
Prior art keywords
bleaching
pulp
carried out
stage
peroxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000443564A
Other languages
French (fr)
Inventor
Steve Moldenius
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Valmet AB
Original Assignee
Sunds Defibrator AB
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sunds Defibrator AB filed Critical Sunds Defibrator AB
Application granted granted Critical
Publication of CA1234655A publication Critical patent/CA1234655A/en
Expired legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10Bleaching ; Apparatus therefor
    • D21C9/16Bleaching ; Apparatus therefor with per compounds
    • D21C9/163Bleaching ; Apparatus therefor with per compounds with peroxides

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

ABSTRACT
A method of peroxide bleaching lignocellulose-containing material for providing a pulp of both high strength and brightness is described. Increase in strength is provided in a first stage by hyper-alkaline peroxide bleaching known per se, i.e. bleaching carried out at an initial pH of over 12, measured in the bleach-ing liquid at 24°C before mixing into the pulp. The desired brightness increase is provided in a subsequent stage with or without intermediate washing of the pulp and at a lower initial pH.

Description

.. ` ~;~3~S5 Method of peroxide bleaching cellulose-containing material DE:SCRIPTION
The present invention relates to peroxide bleaching of lignocellulose-containing material, particularly mechanical and mechano-chemical pulp. Peroxide bleaching is normally carried out solely in one step and for in-creasing the brightness of the pulp. (In certain cases,e.g. for fluff, the intention may also be to improve the water absorption ability). It is known that the pulp properties are then altered a little, the density, smooth-ness and strength increase. It has also been found that strength and smoothness can be increased considerably in peroxide bleaching with high initial pH: tensile index by 50 ~ and Scott Bond by 150 ~. The disadvantage in bleach-ing with an initial pH level above the one which is optimum for brightness, i.e. so-called hyper-alkaline l~eroxide bleaching (HAPs) is that brightness becomes relatively low in relation to the peroxide charge.
The present invention relates to producing a pulp by peroxide bleaching, which is both strong and bright. This result is obtained in accordance with the invention, in principle by bleaching being carried out in two stages at differen~ pH values. In the first stage, which may be denoted HAPB, bleaching is carried out at a high pll (over 12), great strength thus b~ing achieved.
In the second stage peroxide bleaching takes place at a lower pH value more favourable to high brightness.
There are two main implementations of this method. The one consists in that an acid, e.g. sulphuric ~cid, is added towards the end of a HAPB, e.g. after one houj- s bleaching time, to lower the pH to a level where the remaining peroxide may be used for bleaching (~or a~out one hour). There is then obtained a pulp which has greatly improved streng~h and surface ~ 3~6~5 properties and a brightness which is (nearly) the same, in relation to the peroxide charge, as would be obtained in a standard brightness bleaching.
The second implementation which is the one preferred, is a 2-stage bleaching, strength and surface smoothness being obtained in the first stage and desired brightness in the second stage. The second stage can take place with or without intermediate washing (i.e. only with drawal). Bleaching in the second step heavily improves bri~htness for very small peroxide consumption.
It will be seen from the following tables what brightness values are obtained in normal peroxide bleach-ing and hyperalkaline peroxide bleaching ~table 1), and wl1at brightness values are obtained after the s~cond bleaching stage (table 2) in a method in accG~dance with t}~e invention using the second implementation of the method and the same pulps.
Table 1 Bri~htncs:, after bleaching of groundwood (SGW) and thermomachanical pulp (TMP), respectively, to maximum brightness (standard bleaching) and to high strength, hyper-alkaline peroxide bleaching (HAPB), i.e. with an initial pH of 13. The peroxi~e consump-tion is given in parentheses.
Peroxide charge 4 ~, time 120 minutes and temperature 60C
Brightness according to IS0 Standard bleaching _ HAPB
SGW 78.7 (2.3 ~) 75.1 (3.0 ~) TMP 78.6 (2.5 %) 74.7 (2.8 %) Table 2 Brightness according to ISO after peroxide bleach-ing of a hyper-alkaline peroxide bleached (HAPB) pulp. Brightness after HAPB see table 1. Peroxide cons~l~ption in the second step is given in parenthesis.

~34655 Second stage bleaching 1 ~ 2 % 4 % peroxide charge in SGW 81.9 (0,1 %) 83.3 (0.1 %) 2nd stage TMP - 80.0 (0.9 %) 81-6 (0-5 ~) After the second stage bleaching, pulps were obtained with greatly improved strength and surface properties, and with very high brightness. Note that the brightrless is very much higher than what may normally be obtainsd in a standard bleaching (table 1). The peroxide consumptions in the second stage are very small and the optimum bleaching pH is somewhat lower than for a first stage standard bleaching.
The strength and smoothness of the pulps are not notably affected by the 2-stage bleaching, i.e. they retain the high strength and roughness which is the rcsult of the hyper-alkaline peroxide bleaching.
As has been discussed above, the bleaching in the first stage is carried out with an initial pH of over 12, a~ or over 13. The peroxide charge may then be 1 - 8 ~, suitably 2 - 4 ~ (on the amount of dry pulp).
The second stage is generally carried out with an initial pH which is 1 - 2 units lower than the initial p~l in a first stage. For example, it may be in the range 10 - 12, preferably 11 - 11.5. The peroxide charge, when the second implementation of the method is used, may be 1 - 8 %, suitably 2 - 4 ~ reckoned on the dry pulp.
soth stayes can be carried out at a pulp concentra-tion of 7 - 35 %, preferably 10 - 15 %, suitably 11 -12 ~, e.g. in a bleaching tower and at a temperature of 30 ~0 - 95C.
The invention is more closely clarified by the following implementation examples.
The following bleaching technique has been used in the experiment described below.
The initial pH optimum was determined first in rclation to brightness for a given peroxide charge. This --` 1;23~5 can be done in the following way, for example: 1~ grams bone-dry pulp is slurried warm (SCAN M 10: 76 ) in deionized water (or the like~. 0.1 % DTPA, counted on the pulp, is added during slurrying. The pulp is dewatered on a wire gauze on a Buchner funnelO The filtrate is returned to the funnel and filtrated thxough the previously formed pulp cake for recovering the fine material which goes through during the first dewatering step. This is repeated until the filtrate is free from fine material ~i.e. it is clear and often slightly coloured). The pulp is then put into a plastic bag which is sealed (plastic welded) and put into a water bath for being heated to the bleach-ing temperature (most often 60C)o The bleaching chemicals, whicll are commercial silicate (most often 4 ~ of the pulp) magnesium sulphate (most often 0.1 % of the pulp) and alkali to the intended initial pH are mixed in a plastic jar and heatsd to bleaching temperature. The peroxide at room temperature is added to the chemical mixture immediately before mixing into the pulp. By 'initial pH" is intended here the pH in the chemicai mixture at 24C, including the dilution water and the amount of water contained in the wet pulp, but exclud-ing the pulp itself. The dilution water quantity is adjusted such that the pulp concentration after the chemicals are mixed in will be the correct one, most often 15 ~. The bag with the heated pulp is opened and the bleaching chemicals are added. The pulp is subseq~ertly kneaded intensively so that homogenous blendin-l is obtained. The bag is sealed and returned to the water bath. After 5 and 15 minutes' bleaching time the pulp is kneaded further.
Bleaching takes place in a water bath, most often at 60C and during 120 minutes. The bleaching time is the time from mixing in the bleaching chemicals to the time for washing with deionized water, which is at room temperature. The bag is taken out of the water 3~L6~S
.

bath some minutes before full bleaching time and opened, a sample then being taken out for residue chemical analysis. In order to prevent pulp coming out together with residue chemicals, the iiquid is pressed out through a fine wire gauze. Final pH is measured at room temperature and residue peroxide is determined with the aid of iodine titration. The pulp is put in a Buchner funnel and washed with about 6 litres of deioniæed water in accordance with the method described for slushing. The washed pulp is then slushed with a minor quantity of deionized water and the suspension is titrated down to about pH 5 - 6. The pulp is analyzed according to applicable SC~N methods.
3y repeating these bleachings with varying initial pH, the relationship between brightness and initial ~H may ~e determined.
_xample 1 (addition of acid) I bleaching is carried out at a higher initial ~ll, e.g. 13, than what is optimum with relation to brightness, so-called hyper-alkaline peroxide bleaching lllAPB), obtained a pulp which has obtained strength and smoothness increases from the bleaching but with bright-ness which is not optimum in relation to the peroxide charge. IE an acid, e.g. sulphuric acid, is added aft~r a HAPB to the suspension of pulp and bleaching chemical, so that the bleaching liquor pH is lowered to 12, for example, and the bleaching is allowed to continue for a further 60 minutes before termination according to the method given above, a brightness is obtained which is practically the same as with bleaching for optimum brightness. The pulp is then both strong and smooth.
The results from bleaching carried out with an acid will be seen from table 3.
Example 2 (two-stage bleaching~
Hyper-alkaline peroxide bleaching is performed first, e.g. 4 ~ H2O2 and an initial pH of 13. A new peroxide bleaching is subsequently carried out with or without intermediate washing, ancl this can be done in the following manner:
a) With washing After hyper-alkaline peroxide bleaching with washing, bleaching is performed again, e.g. with a 4 %
peroxide charge, with the intention of increasing brightness. For the second bleaching step performed with the same technique as the first, the initial pH
must be optimated with relation to brightness. The optimum initial pH in the second step was 11.5, i.e. a half unit lower than what is optimum for a single stage bleach~ng.
b) Without washint3 The second stage can also be carried out without intermediate washing. Peroxide is then added to the pulp suspension, and possibly acid to obtain optimum pll.
A small amount of the bleaching liquid may possibly be pressed out before the addition of peroxide, so that the pulp concentration will not be too low. Bleaching is then allowed to continue for a further 120 minutes, for example. A pulp is then obtained with increased strength and smoothness and with very high brightness, higher than what can be achieved in one stage optimalized for brightness.
The results from bleachings carried out thus will be seen from table 3.

~3~55 X
8 x Ln ~D
o o .-t~R j~ o r~
h ~ N O

u~O~ O O 00 U
~ .
+ ~ O

R~ ~ . a~ o o ~ N

~ O -- O

u~ a~ u), .
R ~ '. ~ o o oo N

, O ,~ ~
111 U~ ~ ~ N I
Q~
U~
a) ~
~ , O O
O ` ,~ ~ i~ ~DO O o~ I
.
m ~ ~ ~ o o ~3 ~ ~
u ~

a ~ ~" o ,~ ~ o o ul ~ ~ o ~ a) m Q~
,~ x ~a . tn ~ ~ ~ O ~ ~
O
u o m ~ ~ ~

Claims (21)

The embodiments of the convention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of peroxide bleaching lignocellulose-containing material for providing a pulp of both high strength and brigthness, characterized in that the strength increase is achieved in a first stage by hyper-alkaline peroxide bleaching carried out at an initial pH of over 12, measured in the bleaching liquor at 24°C before mixing into the pulp, and in that the desired brightness increase is subsequently achieved in a following stage with or without intermediate washing of the pulp and at a lower initial pH.
2. Method as claimed in claim 1, characterized in that the initial pH in the second stage is 1 - 2 units lower than the initial pH in the first stage.
3. Method as claimed in claim 1, characterized in that the initial pH in the second stage, measur-ed in the bleaching liquid at 24°C before mixing into the pulp attains to 10 - 12.
4. Method as claimed in claim 1, characterized in that the first stage is carried out with a peroxide charge of 1 - 8%, calculated on the quantity of dry pulp and at an initial pH of over 13.
5. Method as claimed in claim 4, characterized in that the pulp is washed after the first stage and that the second stage is carried out with a peroxide charge of 1 - 8%, counted on the quantity of dry pulp and at a pH of at most 11.5.
6. Method as claimed in claim 4, characterized in that both stages are carried out as two separate bleaching steps by the pulp being charged with further peroxide after the first stage has been completed without washing, the pH in the pulp suspension being lowered, and the bleaching subsequently completed for obtaining optimum brightness.
7. Method as claimed in claim 6, characterized in that bleaching liquid is pressed out after the first stage.
8. Method as claimed in claim 6, characterized in that the pH of the bleaching liquid is lowered at least to 12 by the addition of acid.
9. Method as claimed in claim 6, characterized in that bleaching is carried out in a bleaching tower at a pulp concentration of 7 - 35%.
10. Method as claimed in claim 1, 2 and 3, charac-terized in that bleaching is carried out in a bleaching tower at a pulp concentration of 7 -35%.
11. Method as claimed in claims 4, 5 or 7, charac-terized in that bleaching is carried out in a bleaching tower at a pulp concentration of 7 -35%.
12. Method as claimed in claim 8, characterized in that bleaching is carried out in a bleaching tower at a pulp concentration of 7 - 35%.
13. Method as claimed in claim 9, characterized in that bleaching is carried out at a temperature of 40 - 95°C.
14. Method as claimed in claims 1, 2 or 3, charac-terized in that bleaching is carried out at a temperature of 40 - 95°C.
15. Method as claimed in claims 4, 5 or 6, charac-terized in that bleaching is carried out at a temperature of 40 - 95°C.
16. Method as claimed in claims 7, 8 or 99 charac-terized in that bleaching is carried out at a temperature of 40 - 95°C.
17. Method as claimed in claim 12, characterized in that bleaching is carried out at a temperature of 40 - 95°C.
18. Method as claimed in claims 1, 2 or 3, charac-terized in that the pulp is charged with silicate in an amount of 2 - 6%, calculated on the amount of dry pulp.
19. Method as claimed in claims 4, 5 or 6, charac-terized in that the pulp is charged with silicate in an amount of 2 - 6%, calculated on the amount of dry pulp.
20. Method as claimed in claims 79 8 or 9, charac-terized in that the pulp is charged with silicate in an amount of 2 - 6%, calculated on the amount of dry pulp.
21. Method as claimed in claims 12, 13 or 17, characterized in that the pulp is charged with silicate in an amount of 2 - 6%, calculated on the amount of dry pulp.
CA000443564A 1982-12-17 1983-12-16 Method of peroxide bleaching cellulose-containing material Expired CA1234655A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8207236-4 1982-12-17
SE8207236A SE452346C (en) 1982-12-17 1982-12-17 PROCEDURES FOR PEROXID WHITING OF LIGNOCELLULOSALLY MATERIAL IN TWO STEPS

Publications (1)

Publication Number Publication Date
CA1234655A true CA1234655A (en) 1988-04-05

Family

ID=20349053

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000443564A Expired CA1234655A (en) 1982-12-17 1983-12-16 Method of peroxide bleaching cellulose-containing material

Country Status (13)

Country Link
US (1) US4734160A (en)
EP (1) EP0128190B1 (en)
JP (1) JPS60500263A (en)
AT (1) ATE36565T1 (en)
BR (1) BR8307656A (en)
CA (1) CA1234655A (en)
DE (1) DE3377724D1 (en)
ES (1) ES528138A0 (en)
FI (1) FI843242A0 (en)
IT (1) IT1197760B (en)
NO (1) NO163631C (en)
SE (1) SE452346C (en)
WO (1) WO1984002366A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE455203B (en) * 1986-10-20 1988-06-27 Eka Nobel Ab PROCEDURE FOR THE CONTROL OF PEROXID WHEATING OF MASS
FR2673813B1 (en) * 1991-03-15 1995-02-24 Atochem TWO-STEP BLEACHING PROCESS OF PLANT MATERIAL FOR FOOD USE.
CA2063351C (en) * 1992-03-18 1996-08-13 Stanley Alan Heimburger Process for bleaching hardwood pulp
SE500616C2 (en) * 1993-06-08 1994-07-25 Kvaerner Pulping Tech Bleaching of chemical pulp with peroxide at overpressure
US7052578B2 (en) * 2000-01-28 2006-05-30 Martin Marietta Magnesia Specialties, Inc. Process employing magnesium hydroxide in peroxide bleaching of mechanical pulp
US6899790B2 (en) 2000-03-06 2005-05-31 Georgia-Pacific Corporation Method of providing papermaking fibers with durable curl
US6627041B2 (en) * 2000-03-06 2003-09-30 Georgia-Pacific Corporation Method of bleaching and providing papermaking fibers with durable curl
US7297225B2 (en) * 2004-06-22 2007-11-20 Georgia-Pacific Consumer Products Lp Process for high temperature peroxide bleaching of pulp with cool discharge
FI122238B (en) * 2006-02-09 2011-10-31 Metso Automation Oy Method and apparatus for determining the total peroxide content of a pulp suspension
US8673113B2 (en) 2010-06-09 2014-03-18 The University Of British Columbia Process for reducing specific energy demand during refining of thermomechanical and chemi-thermomechanical pulp

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3966542A (en) * 1974-09-20 1976-06-29 General Signal Corporation Multi-stage bleaching of pulp using successively lower power levels
SE413684C (en) * 1974-09-23 1987-05-18 Mo Och Domsjoe Ab PROCEDURE FOR PREPARING CELLULOSAMASSA IN THE REPLACEMENT AREA 65-95%
SE387977B (en) * 1975-01-27 1976-09-20 Elektrokemiska Ab WAY TO PRODUCE BLEACH, MECHANICAL PULP WITH HIGH STRENGTH AND BRIGHTNESS
SE407091B (en) * 1976-02-05 1979-03-12 Sca Development Ab WAY TO PEROXIDE BLEACHING THROUGH REFINING CELLULOSE PULP
NO144711C (en) * 1978-04-04 1981-10-21 Myrens Verksted As PROCEDURE FOR BLACKING OXYGEN-EQUIVALIZED CELLULOSE-containing OZONE

Also Published As

Publication number Publication date
US4734160A (en) 1988-03-29
SE8207236D0 (en) 1982-12-17
FI843242A (en) 1984-08-16
BR8307656A (en) 1984-12-11
SE8207236L (en) 1984-06-18
SE452346C (en) 1990-03-26
ATE36565T1 (en) 1988-09-15
IT1197760B (en) 1988-12-06
IT8349543A0 (en) 1983-12-19
ES8505001A1 (en) 1985-04-16
NO163631B (en) 1990-03-19
ES528138A0 (en) 1985-04-16
NO843255L (en) 1984-08-15
NO163631C (en) 1990-06-27
DE3377724D1 (en) 1988-09-22
FI843242A0 (en) 1984-08-16
JPS60500263A (en) 1985-02-28
EP0128190A1 (en) 1984-12-19
SE452346B (en) 1987-11-23
EP0128190B1 (en) 1988-08-17
WO1984002366A1 (en) 1984-06-21

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